Platinum group metal-free catalysts for reducing the ignition temperature of particulates on a diesel particulate filter

ABSTRACT

A catalyzed diesel particulate filter (CDPF) and a method for filtering particulates from diesel engine exhaust are provided, where the catalyzed diesel particulate filter includes a substrate and a catalyst composition, where the catalyst composition contains at least one first component, at least one second component, and at least one third component, where the first component is at least one first component selected from the group consisting of cerium and a lanthanide and mixtures thereof, the at least one second component is selected from the group consisting of cobalt, copper, manganese and mixtures thereof; and the third component comprises strontium, where the first component, the second component, and the third component are in an oxide form after calcination. The catalyst on the catalyzed diesel particulate filter lowers the temperature at which particulates are removed from the CDPF by oxidizing the particulates on the filter. The catalyzed diesel particulate filter may also include a washcoat. Washcoats prepared from colloidal aluminum oxide may have higher surface areas and pore volumes loadings than washcoats containing aluminum oxide prepared from aluminum nitrate.

RELATED APPLICATIONS

This application claims the benefit under 35 U.S.C. §119(e) of U.S.Provisional Application Nos.: 60/619,382; 60/619,390; and 60/619,314,all filed on Oct. 14, 2004, all of which are incorporated herein byreference in their entirety.

This application is a divisional application under 35 USC §121 of U.S.application Ser. No. 11/251,372, which is still pending.”

FIELD OF THE INVENTION

Embodiments of the present invention relate to platinum group metal(PGM)-free catalyst compositions for reducing the ignition temperatureof particulates on a diesel particulate filter.

BACKGROUND

Diesel engines for motor vehicles have good fuel economy and highdurability. Unfortunately, the exhaust gas from diesel engines containshigh levels of NO_(x) and particulates. Both the United States andEurope have enacted regulations with strict limits on NO_(x) andparticulate emissions from diesel engines. The particulate and NO_(x)limits as of 2004 for US trucks are 0.1 g/bhp-hr and 2 g/bhp-hr,respectively. The limits decrease to 0.01 g/bhp-hr and 0.2 g/bhp-hr in2007.

Diesel particulate filters (DPFs) have been installed on buses anddiesel automobiles for many years to remove the particulates from theexhaust stream. The filters may become plugged due to the buildup ofparticulates on the filter. The pressure drop through the filter mayincrease as the particulate levels on the filter increase. The pluggedfilter may have to be regenerated or replaced.

The particulates may comprise a mixture of lube oil solids, carbonparticulates, and inorganic ash. The lube oil solids and carbonparticulates can sometimes be removed from the DPF through combustion.The ignition temperature of the carbon particulates is normally about600° C. Diesel exhaust temperatures are rarely that high. The exhaustgas temperature can be increased by retarding the timing but at the costof fuel efficiency. Alternatively, the filter can be heated with anelectric heater. Heating the electric heater requires energy, with anaccompanying fuel efficiency penalty.

Johnson Matthey has described a system called “Continuously RegeneratingTrap” (“CRT™”). A platinum-based diesel oxidation catalyst (DOC) isplaced upstream of the DPF to oxidize NO in the exhaust stream to NO₂.The NO₂ in the exhaust stream may oxidize the carbon particles and lubeoil solids on the DPF at lower temperatures than does the oxygen in thediesel exhaust gas. The CRT™ system is described, for example, in U.S.Pat. No. 4,902,487 to Cooper et al.

The platinum in the CRT™ DOC is expensive. Further, platinum catalystsmay be poisoned by sulfur in the diesel fuel. Low sulfur diesel fuel iscostly.

Catalysts have been dissolved or suspended in diesel fuel to lower thecombustion temperature of the carbon particulates on the DPF. Use offuel-borne catalysts requires additional components such as a tank forthe fuel additive, a dosing system, and infrastructure to fill theadditive tank. The fuel-borne additive can be expensive, particularly ifthe fuel-borne additive is a platinum group metal (PGM). Further, thefuel-borne additive can form particulate particles that may accumulateon the DPF, making it necessary to change the DPF.

Placing a catalyst on the DPF to lower the ignition temperature of theparticles may be an attractive alternative to a fuel-borne catalyst.Hartwig (U.S. Pat. No. 4,510,265) describes a catalyst comprising aplatinum group metal and silver vanadate. The catalyst of Homeier (U.S.Pat. No. 4,759,918) comprises platinum, palladium, or rhodium on asulfur resistant support such as titania or zirconia. Dettling (U.S.Pat. No. 5,100,632) utilizes a catalyst that is a mixture of one or moreplatinum group metals and one or more alkaline earth oxides such asmagnesium oxide. The catalysts of Harwig, Homeier, and Dettling al.comprise platinum group metals (PGMs). Platinum group metal (PGM)catalysts are expensive.

DPF's that contain vanadium catalysts to lower the combustiontemperature of the carbon particulates have been described in U.S. Pat.No. 4,900,517 to DeGussa A. G. Other vanadium catalysts are discussed inU.S. Pat. No. 6,013,599, assigned to Redem.

Vanadium oxides are volatile and toxic. The high temperatures that arepresent in the DPF during combustion of the carbon particulates canvaporize the vanadium catalysts on the DPF, potentially leading tohealth problems in the general populace. There is a need for DPFcatalysts that do not contain expensive PGMs or toxic vanadiumcompounds.

The surface area of many DPF catalysts is low. Adding a washcoat to theDPF to support the catalyst can increase the surface area of thecatalyst by dispersing the catalyst on the washcoat. There is a need fora washcoat that can be placed on the support to increase the surfacearea of the supported DPF catalyst.

SUMMARY OF THE INVENTION

One aspect of the present invention concerns a catalyst composition forreducing the ignition temperature of particulates from diesel exhaust.The catalyst composition contains:

a) at least one first component selected from the group consisting ofcerium, a lanthanide, and mixtures thereof;

b) at least one second component selected from the group consisting ofcobalt, copper, manganese and mixtures thereof; and

c) at least one third component containing strontium, where the firstcomponent, the second component, and the third component are in an oxideform after calcination.

Advantageously, when the second component contains cobalt, a molar ratioof the first component to the second component to the third componentmay be in a range of 35-70:5-45:5-35; and when the second componentcontains manganese, a molar ratio of the first component to the secondcomponent to the third component may be in a range of 15-60:30-70:5-35.Preferably, when the second component contains a combination ofmanganese and copper, a molar ratio of manganese to copper may be in arange of 30-95 to 70-5.

Another aspect of the present invention concerns a catalyzed dieselparticulate filter containing a substrate for filtering particulatesfrom diesel engine exhaust; and a catalyst composition, where thecatalyst composition contains:

a) at least one first component selected from the group consisting ofcerium, a lanthanide, and mixtures thereof;

b) at least one second component selected from the group consisting ofcobalt, copper, manganese and mixtures thereof; and

c) at least one third component containing strontium, where the firstcomponent, the second component, and the third component are in an oxideform after calcination.

Advantageously, the substrate is selected from the group consisting of awoven fabric, a wire mesh, a disk filter, a ceramic honeycomb monolith,a ceramic foam, a metallic foam, and a wall flow filter. Preferably, thesubstrate may be made from a material selected from the group consistingof a metal, alumina, silica alumina, cordierite, silicon nitride,silicon carbide, sodium zirconium phosphate, and mullite.

In an embodiment, when the second component contains cobalt, a molarratio of the first component to the second component to the thirdcomponent may be in a range of 35-70:5-45:5-35; and when the secondcomponent contains manganese, a molar ratio of the first component tothe second component to the third component may be in a range of15-60:30-70:5-35. Advantageously, the first component, the secondcomponent, and the third component may initially be in the form ofwater-soluble salts. Preferably, the water-soluble salts may bedissolved in water to form an aqueous solution, and the aqueous solutionmay be impregnated into the substrate.

In an embodiment, the substrate may be calcined after the aqueoussolution is impregnated into said substrate, thereby forming thecatalyst composition. Advantageously, a loading of the catalystcomposition on the catalyzed diesel particulate filter may be in a rangeof approximately 5 g/L to approximately 90 g/L, where the loading is onthe basis of the oxides. In an embodiment, the catalyzed dieselparticulate filter may also contain a washcoat on the substrate.Preferably, the catalyst composition may be supported on the washcoat.Advantageously, the washcoat may contain aluminum oxide. In anembodiment, the aluminum oxide may be applied to the substrate in a formof colloidal alumina.

In an embodiment, the colloidal alumina may be prepared with nanoparticle technology. Preferably, a loading of the washcoat may be in arange of approximately 5 g/L to approximately 100 g/L. In anotherembodiment, the aluminum oxide may be produced from aluminum nitrate.Advantageously, the washcoat may also contain at least one oxideselected from the group consisting of silica alumina, a zeolite, silica,cerium oxide, lanthanide oxide, zirconium oxide, and mixtures thereof.

Yet another aspect of the present invention concerns a method ofremoving particulates from exhaust gas from a diesel engine. The methodmay include contacting the exhaust gas with a catalyzed dieselparticulate filter, thereby removing the particulates from the exhaustgas, where the catalyzed diesel particulate filter may contain asubstrate and a catalyst composition, where the catalyst compositioncontains:

a) at least one first component selected from the group consisting ofcerium and a lanthanide; and

b) at least one second component selected from the group consisting ofcobalt, copper, manganese and mixtures thereof; and

c) at least one third component containing strontium, where the firstcomponent; the second component, and the third component are in an oxideform after calcination.

Advantageously, when the second component contains cobalt a molar ratioof the first component to the second component to the third componentmay be in a range of 35-70:5-45:5-35; and when the second componentcontains manganese, a molar ratio of the first component to the secondcomponent to the third component may be in a range of 15-60:30-70:5-35.

Preferably, a loading of the catalyst composition on the catalyzeddiesel particulate filter may be in a range of approximately 10 g/L toapproximately 60 g/L, where the loading is on the basis of the oxides.In an embodiment, the catalyzed diesel particulate filter may alsocontain a washcoat. Preferably, the washcoat contains aluminum oxide.Advantageously the washcoat may also contain at least one oxide selectedfrom the group consisting of silica alumina, a zeolite, silica, ceriumoxide, lanthanide oxide, zirconium oxide, and mixtures thereof.

In an embodiment, the method may also include removing at least aportion of the particulates from the catalyzed diesel particulate filterby contacting the catalyzed diesel particulate filter with an oxidizinggas. Preferably, the oxidizing gas may be selected from the groupconsisting of O₂, NO, and NO₂. Advantageously, the catalyzed dieselparticulate filter may be contacted with the oxidizing gas at atemperature of approximately 100° C. to approximately 800° C.Preferably, contacting the exhaust gas with the diesel oxidationcatalyst may be before contacting the exhaust gas with the catalyzeddiesel particulate filter.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a series of graphs of the CO₂ concentration versustemperature for diesel particulate filter substrates with soot loadingsof about 2 g/L;

Curve 1A is a curve for a blank, a substrate that does not contain acatalyst according to an embodiment of the invention; and

Curve 1B is a curve for a substrate with a catalyst according to anembodiment of the invention;

FIG. 2 shows a series of graphs of the CO₂ concentration versustemperature for diesel particulate filter substrates with a soot loadingof about 2 g/L and various loadings of a catalyst composition accordingto an embodiment of the invention;

Curve 2A is a curve for a substrate with a catalyst loading of 5 g/L;

Curve 2B is a curve for a substrate with a catalyst loading of 10 g/L;

Curve 2C is a curve for a substrate with a catalyst loading of 30 g/L;

Curve 2D is a curve for a substrate with a catalyst loading of 60 g/L;

Curve 2E is a curve for a substrate with a catalyst loading of 90 g/L;and

Curve 2F is a curve for a blank, a substrate that does not contain acatalyst;

FIG. 3 shows a series of graphs of the BET surface area in m²/g versuswashcoat loading in g/L;

Curve 3A is a curve for an aluminum oxide washcoat prepared fromaluminum nitrate; and

Curve 3B is a curve for an aluminum oxide washcoat prepared withcolloidal alumina;

FIG. 4 shows a series of graphs of the pore volume in cm³/g versuswashcoat loading in g/L for aluminum oxide washcoats;

Curve 4A is a curve of the pore volume versus loading for an aluminumoxide washcoat prepared from aluminum nitrate; and

Curve 4B is a curve of the pore volume versus loading for an aluminumoxide washcoat prepared with colloidal alumina;

FIG. 5 shows a series of graphs of the CO₂ concentration in ppm versustemperature in degrees Centigrade for various combinations of substratesand catalysts according to embodiments of the present invention;

Curve 5A is a curve for a blank, a substrate with no catalyst;

Curve 5B is a curve for a substrate with a fresh catalyst according toan embodiment of the invention; and

Curve 5C is a curve for a substrate with the catalyst of curve 5B afterhydrothermal aging at 850° C. for 16 hours;

FIG. 6 shows a series of graphs of the CO₂ concentration in ppm versustemperature in degrees Centigrade for various combinations of substratesand catalysts according to embodiments of the present invention;

Curve 6A is a curve for a blank, a substrate with no catalyst

Curve 6B is a curve for a substrate with a fresh catalyst according toan embodiment of the invention;

Curve 6C is a curve for a substrate with the catalyst of Curve 6B afterhydrothermal aging at 850° C. for 16 hours;

Curve 6D is a curve for a substrate impregnated in two stages, a firststage impregnation with a solution comprising colloidal alumina, and asecond stage impregnation with a solution comprising a catalystcomposition according to an embodiment of the invention;

Curve 6E is a curve for a substrate impregnated in two stages, as forCurve 6D, after hydrothermal aging at 850° C. for 16 hours;

Curve 6F is a curve for a substrate impregnated with a single solutioncomprising both colloidal alumina and a catalyst composition accordingto an embodiment of the invention; and

Curve 6G is a curve for a substrate impregnated with a single solution,as for Curve 6F, after hydrothermal aging at 850° C. for 16 hours.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Embodiments of the present invention provide catalyst compositions andmethods for lowering the ignition temperature of particulates on dieselparticulate filters (DPFs). The catalyst compositions may not containplatinum group metals (PGMs) or vanadium, though PGMs or vanadium may beadded to the catalyst composition in some embodiments. PGMs areexpensive, and vanadium compounds are volatile and toxic. The catalystcompositions may be supported on a washcoat on the DPF in someembodiments. Some embodiments of the washcoat may provide increasedhydrothermal stability to the catalyst composition, as shown in theexamples below.

The particulate matter on the DPF may comprise three main fractions, asolid fraction, a soluble organic fraction, and sulfates. The solidfraction may comprise about 54% of the particulate matter, the solubleorganic fraction about 32% of the particulate matter, and the sulfatesabout 14% of the particulate matter.

The solid fraction (hereafter SOL) may comprise about 41% carbon andabout 13% ash, a total of about 54% of the particulate matter. Thecarbon may have an ignition temperature of about 600° C. or higher, inthe absence of a catalyst.

The soluble organic fraction (hereafter SOF) may comprise about 7% fuelSOF and 25% lube SOF, a total of about 32% of the particulate matter.The SOF may have an ignition temperature of about 350° C., in theabsence of a catalyst.

A complex series of reactions may take place when the DPF is regeneratedby oxidizing the particulates. The carbon can be removed from the DPFwith the following reactions:

C+O₂═CO₂

C+O₂═CO

C+NO₂═CO+NO

C+2NO₂═CO₂+2NO

The reactions of carbon with NO₂ (nitrogen dioxide) may occur morerapidly and at a lower temperature than the reactions of carbon with theO₂ in the exhaust gas. High concentrations of NO₂ in the exhaust streammay therefore increase both the efficiency and the rate of carbonremoval from the DPF.

A diesel oxidation catalyst (DOC) may be placed upstream of the DPF tocatalyze the following reactions:

CO+½O₂═CO₂

NO+½O₂═NO₂

Oxidizing the carbon monoxide in the exhaust gas to carbon dioxide maydecrease the CO levels in the exhaust gas. The low CO concentration inthe exhaust gas after the exhaust gas passes through the DOC may bebeneficial in helping to meet CO emission limits. Oxidizing the NO inthe exhaust gas to NO₂ may increase the concentration of NO₂ in theexhaust gas. The high NO₂ concentration in the exhaust gas after theexhaust gas passes through the DOC may improve the efficiency of carbonremoval from the DPF.

Placing a catalyst composition according to embodiments of the presentinvention on the DPF to form a catalyzed diesel particulate filter(CDPF) may lower the temperature at which the DPF may be regenerated byoxidizing the particulates on the DPF. The catalyst compositionsaccording to embodiments of the invention may comprise at least onefirst component selected from the group consisting of cerium, alanthanide, and mixtures thereof, at least one second component selectedfrom the group consisting of cobalt, copper, manganese, and mixturesthereof, and at least one third component comprising strontium. Thecatalyst composition may also comprise other components, including, butnot limited to, one or more components to stabilize the surface area ofthe first component selected from the group consisting of cerium, alanthanide, and mixtures thereof.

When the second component comprises cobalt, the catalyst composition maycomprise the first component, the second component, and the thirdcomponent in a molar ratio of approximately 60:15:25. The molar ratiocan be in a range of 35-75:5-45:5:35, more preferably 40-70:10-30:10-30,and most preferably 55-65:10-20:20-30.

When the second component comprises manganese, the catalyst compositionmay comprise the first component, the second component, and the thirdcomponent in a molar ratio of approximately 35:50:15. The molar ratiocan be in a range of 15-60:30-70:5:35, more preferably25-45:40-60:10-30, and most preferably 30-40:45-55:10-20.

In an embodiment where the second component comprises copper in additionto manganese the molar ratio of manganese and copper comprising thesecond component can be in a range of approximately 80:20. The molarratio can be in a range of 30-95:70:5, more preferably 50-95:50:5, andmost preferably 70-95:30:5.

The ranges of the molar ratios of the first component, the secondcomponent, and the third component may be the same when the secondcomponent comprises a mixture of copper and manganese as when the secondcomponent comprises manganese without copper.

In an embodiment, the cerium component may comprise CeO₂. The lanthanidecomponent can comprise Ln₂O₃, where Ln is at least one lanthanide. In anembodiment, the cobalt component can comprise CO₃O₄. In an embodiment,the strontium component can comprise SrO. The copper component maycomprise Cu₂O or CuO. The manganese can comprise Mn₂O₃, MnO₂, ormixtures thereof. Other oxides or compounds of cerium, lanthanides,cobalt, manganese, and strontium may be utilized in alternativeembodiments. Complex oxides of cerium oxide, lanthanide oxide, cobaltoxide, copper oxide, manganese oxide, and strontium oxide may also besuitable.

The DPF may comprise a substrate. The substrate of the DPF can be anysuitable filter for particulates. Some suitable forms of substrates mayinclude woven filters, particularly woven ceramic fiber filters, wiremeshes, disk filters, ceramic honeycomb monoliths, ceramic or metallicfoams, wall flow filters, and other suitable filters. Wall flow filtersare similar to honeycomb substrates for automobile exhaust gascatalysts. They may differ from the honeycomb substrates that may beused to form normal automobile exhaust gas catalysts in that thechannels of the wall flow filter may be alternately plugged at an inletand an outlet so that the exhaust gas is forced to flow through theporous walls of the wall flow filter while traveling from the inlet tothe outlet of the wall flow filter. The particulates may be depositedonto the CDPF and may thereby be removed from the exhaust gas.

The substrate may be made from a variety of materials. Materials thatwithstand high temperatures may be preferable, because burning theparticulates on the filter can subject the substrate to hightemperatures. Some suitable high temperature materials for forming thesubstrate of the diesel particulate filter can include, but are notlimited to, a metal, alumina, silica alumina, cordierite, siliconnitride, silicon carbide, sodium zirconium phosphate, mullite, and otherappropriate high temperature materials known to one skilled in the art.Suitable metals may include, but are not limited to, steels andspecialty steels.

A catalyzed diesel particulate filter (CDPF) may comprise a catalystcomposition according to embodiments of the present invention and a DPF.The catalyst composition may be placed on the DPF to form the CDPF inany suitable manner.

In an embodiment, a loading of the catalyst composition on the catalyzeddiesel particulate filter (CDPF) may be in a range of approximately 5g/L to approximately 90 g/L, where the loading of the catalystcomposition is on the basis of the oxides.

Catalyst loadings of 5 g/L, 10 g/L, 30 g/L, 60 g/L, and 90 g/L may beeffective in reducing the ignition temperature of the particulates onthe catalyzed particulate filter, as shown in the examples below.Loadings of the catalyst composition less than approximately 5 g/L maynot be as effective in reducing the ignition temperature of theparticulates on the catalyzed diesel particulate filter as higherloadings, at least for the catalyst compositions, substrates, andoperating conditions that were tested in the examples.

Successively increasing the catalyst loading on the CDPF from 5 g/L to60 g/L may improve the effectiveness of the oxidation of theparticulates. Further increasing the catalyst loading above 60 g/L maynot significantly improve the effectiveness of the catalyst compositionin oxidizing the particulates, as shown in the examples below. Catalystloadings in the range of 5 g/L to 60 g/L may be optimal, at least forthe embodiments of catalysts and substrates that are described in theexamples. Catalyst loadings above 60 g/L may not be any more effectivein oxidizing the particulate matter on the CDPF than catalyst loadingsin the range of approximately 5 g/L to approximately 60 g/L.

The optimal catalyst loadings on the CDPF may depend on the type ofsubstrate that is used. A range of approximately 5 g/L to approximately60 g/L may be optimal for a cordierite substrate. Different catalystloadings may be optimal for other substrates. Different catalystloadings may also be optimal for other formulations of the catalystcomposition.

Although not wishing to be tied to a theory, it is believed thatsintering of the catalyst composition may take place when the catalystloading on the CDPF is greater than approximately 60 g/L, at least for acordierite substrate and the catalyst compositions that were tested inthe examples below. Sintering of the catalyst composition may reduce theeffectiveness of the catalyst composition in lowering the ignitiontemperature of the particulates on the CDPF.

In an embodiment, a washcoat may be placed onto the DPF. In someembodiments, the catalyst composition may be supported on the washcoat.The washcoat may comprise at least one component selected from the groupconsisting of alumina, silica-alumina, a zeolite, silica, a lanthanide,a mixture of lanthanides, cerium oxide, zirconium oxide, mixtures orsolid solutions of cerium oxide, lanthanide oxide, and zirconium oxide,a stabilizer, and other suitable washcoat components well known to thoseskilled in the art. The washcoat may comprise oxides, precursor salts ofoxides, or a mixture of oxides and precursor salts of oxides.

Advantageously, the washcoat may comprise aluminum oxide. In anembodiment, the aluminum oxide in the washcoat may be prepared fromaluminum nitrate. Calcining the aluminum nitrate may form aluminumoxide. In an alternative embodiment, the aluminum oxide in the washcoatmay comprise colloidal aluminum oxide. Although the aluminum oxide maybe applied to the substrate as colloidal aluminum oxide or alumina, aphase transition may take place in the colloidal alumina when thesubstrate and the alumina washcoat are calcined.

A loading of aluminum oxide in the washcoat on the DPF may be in a rangeof approximately 5 to approximately 100 g/L, more preferablyapproximately 10 g/L to approximately 80 g/L, and most preferablyapproximately 10 g/L to approximately 65 g/L, all on the basis of Al₂O₃.The washcoat may comprise other components in addition to the alumina.In some embodiments, the washcoat may not comprise alumina.

As shown in the examples below, the BET surface areas and the porevolumes of washcoats prepared with colloidal alumina may be higher thanthe BET surface areas and pore volumes of aluminum oxide washcoatsprepared from aluminum nitrate.

It may generally be desirable that washcoats have high BET surface areasand pore volumes. For example, catalysts that are supported on washcoatsthat have high surface areas and pore volumes may have higher surfaceareas and/or activities than catalysts that are supported on washcoatsthat have low surface areas and pore volumes. Forming washcoats withcolloidal alumina may generally be preferable to forming washcoats fromalumina prepared from aluminum nitrate.

In an embodiment, the colloidal alumina may comprise a colloidaldispersion of aluminum oxide. Advantageously, the colloidal dispersionof aluminum oxide may be prepared with nano particle technology. Variousforms of colloidal dispersions of aluminum oxide may be suitable forpreparing washcoats on the DPF substrate.

One suitable form of colloidal alumina may be NYACOL® AL20, commerciallyavailable from Nyacol Nano Technologies, Inc., Ashland, Mass. 01721.NYACOL® AL20 is a 20 wt % dispersion of colloidal alumina with aparticle size of approximately 50 nm. Other forms of colloidal aluminamay also be suitable for forming washcoats on the DPF. Although thealumina may be applied to the substrate as colloidal alumina, calciningthe colloidal alumina may lead to phase changes in the colloidalalumina. The calcined colloidal alumina may comprise, for example,gamma, eta, theta, delta, alpha alumina, or mixtures thereof. Thecalcined colloidal alumina may comprise any suitable phase of alumina.

As shown in the examples below, a washcoat that comprises alumina mayincrease the hydrothermal stability of the catalyst compositionaccording to embodiments of the present invention.

The washcoat may further comprise oxides or precursors of oxides, suchas, but not limited to, cerium oxides, zirconium oxides, zeolites,lanthanide oxides, or mixtures, solid solutions, or complex oxidesthereof. The precursors of the oxides may be converted to thecorresponding oxides when the precursors are calcined.

The first component, the second component, and the third component thatmay form the catalyst composition according to embodiments of thepresent invention may be oxides or salts. The salts may generally beconverted to oxides when calcined.

A variety of precursor salts of the catalyst composition can be used.Some suitable forms of precursor salts for the catalyst composition mayinclude, but are not limited to, chloride salts, nitrate salts, acetatesalts, citrate salts, or acetylacetonate salts. The precursor salts maybe converted into the catalyst composition when the precursors of thecatalyst composition are calcined.

In an embodiment, each of the catalyst composition precursor salts maybe calcined separately to form oxides. The oxides may be mixed to formthe catalyst composition. In an alternative embodiment, two or more ofthe catalyst composition precursor salts may be mixed, and the mixtureof catalyst composition precursor salts may be calcined to form thecatalyst composition. In another embodiment, all of the catalystcomposition precursor salts may be mixed before the mixture is calcined.The mixture of catalyst composition precursor salts may comprise amixture of solid catalyst composition precursor salts, an aqueoussolution of water-soluble catalyst composition precursor salts, or acombination of solid catalyst composition precursor salts and a solutioncontaining water-soluble catalyst composition precursor salts. In anembodiment, the catalyst composition may be formed prior to being placedon the DPF.

In an embodiment, water-soluble precursor salts of the catalystcomposition may be dissolved in water to form an aqueous solution, andthe aqueous solution containing the water-soluble precursor salts of thecatalyst composition may be impregnated into the DPF substrate and/orthe washcoat on the substrate. The aqueous solution of the catalystcomposition precursor salts may be dried to remove the water. Calciningthe catalyst composition precursor salts may convert the precursor saltsinto oxides, thereby forming the catalyst composition. In an embodiment,a washcoat may be placed onto the DPF before, after, or at the same timeas the aqueous solution of the precursor salts is impregnated into theDPF substrate. The aqueous solution may be impregnated into the DPF, thewashcoat, or both the DPF and the washcoat. In some embodiments, thecatalyst composition may be supported on the washcoat on the substrate.

Calcination of the water-soluble salts may convert the water-solublesalts into the corresponding oxides. The calcination may generally beperformed at a temperature of approximately 550° C. The calcination maybe performed at a temperature of approximately 150° C. to approximately850° C., more preferably approximately 200° C. to approximately 800° C.,and most preferably approximately 450° C. to approximately 750° C.

In an embodiment, a precipitating agent may be added to an aqueoussolution comprising at least one water-soluble precursor salt of thecatalyst composition. The at least one catalyst precursor salt may beprecipitated by the precipitating agent.

Suitable precipitating agents may include, but are not limited to,ammonium hydroxide and an alkali hydroxide. Calcining the precipitatedprecursor salt of the catalyst composition may convert the precipitatedprecursor salt of the catalyst composition into the corresponding oxide.The oxide or oxides may be combined with other salts or oxides asdescribed previously to form the catalyst composition.

Other methods of forming the catalyst composition and the washcoat mayalso be suitable. Suitable methods of forming the catalyst compositionand the washcoat are known to those skilled in the art.

In an embodiment, a method is provided for removing particulates fromexhaust gas from a diesel engine. The method may comprise contacting theexhaust gas with a catalyzed particulate filter (CDPF), where thecatalyzed particulate filter comprises a substrate and a catalystcomposition according to an embodiment of the invention. A suitablecatalyst composition may comprise at least one first component selectedfrom the group consisting of cerium, a lanthanide, and mixtures thereofat least one second component selected from the group consisting ofcobalt, copper, manganese, and mixtures thereof, and a third componentcomprising strontium. When the second component comprises cobalt, thefirst component, the second component, and the third component may be ina molar ratio of approximately 60:15:25, more preferably in a molarratio of 55-65:10-20:20-30.

When the second component comprises manganese, the first component, thesecond component, and the third component may be in a molar ratio ofapproximately 35:50:15 more preferably in a molar ratio of30-40:45-55:10-20.

When the second component comprises a combination of manganese andcopper, the molar ratios of the first component, the second component,and the third component may be in the same molar ratios as when thesecond component comprises manganese without copper.

Contacting the exhaust gas and particulates with the CDPF may remove atleast a portion of the particulates from the exhaust gas. Theparticulates may be deposited on the CDPF, thereby removing them fromthe exhaust gas.

Contacting the CDPF and the particulates that were deposited on the CDPFwith an oxidizing gas such as oxygen or NO₂ may remove at least aportion of the particulates from the CDPF by oxidizing the particulateson the CDPF. It is believed that NO may act as an oxidizing gas undersome circumstances. Although not wishing to be bound by a theory, it isbelieved that at least a portion of the NO may be oxidized to NO₂ in thepresence of the catalyst composition of the present invention. In thecontext of this application, NO, NO₂, and O₂ are all considered to beoxidizing gases. The catalyst composition according to an embodiment ofthe invention may reduce the temperature at which the particulates areoxidized when the CDPF and particulates are contacted with the oxidizinggas.

The particulates and CDPF may be contacted with the oxidizing gas attemperatures of approximately 100° C. to approximately 800° C., morepreferably temperatures of approximately 150° C. to approximately 750°C., and most preferably temperatures of approximately 200° C. toapproximately 700° C.

The method may further comprise contacting the exhaust gas with a dieseloxidation catalyst (DOC) before contacting the exhaust gas with theCDPF. Contacting the exhaust gas with the DOC may increase the amount ofNO₂ in the diesel exhaust gas by oxidizing NO to NO₂.

The NO_(x) in the exhaust gas before the exhaust gas passes through theDOC may generally comprise about 5-10% NO and about 90-95% NO₂. Afterpassing through the DOC, the NO in the exhaust gas may compriseapproximately 50% NO and about 50% NO₂. The ratio can, of course, vary,depending on the composition and the operating conditions of the DOC andthe operating conditions of the diesel engine.

Contacting the exhaust gas with the DOC prior to contacting the exhaustgas with CDPF to increase the amount of NO₂ in the exhaust gas prior tocontacting the exhaust gas with the particulates on the CDPF is anotherembodiment of the method of the present invention. The increased NO₂concentration in the exhaust gas after the exhaust gas contacts the DOCmay improve the removal efficiency of particulates from the CDPF.

The following examples illustrate embodiments of various aspects of theinvention. The examples are not meant to be limiting on the scope of theclaims.

EXAMPLES Loading of Soot onto the Substrates

Exhaust gas from a Honda diesel generator (Model No. EB12D) wascontacted with the diesel particulate filter substrates until thesubstrates were loaded with approximately 2 g/L of soot.

Example 1 Measurement of the CO₂ Concentration in the Offgas from theSoot-Loaded Substrate as a Function of Temperature

Soot-loaded DPF substrates were contacted with a gas stream thatcomprised about 10% oxygen, about 8% water, about 150 ppm NO, and about150 ppm NO₂. The temperature of the substrate was increased from 200° C.to 650° C. or 700° C., and the concentration of CO₂ in the exhaust gaswas monitored as a function of temperature.

FIG. 1 shows a graph of the concentration of CO₂ in the exhaust streamversus temperature for a substrate that had been loaded with 2 g/L ofsoot, with and without a catalyst composition according to an embodimentof the invention. FIG. 1A, the lower curve of FIG. 1, is a graph of theCO₂ concentration in the exhaust gas with a blank substrate, asoot-loaded cordierite substrate that does not contain a catalystcomposition according to an embodiment of the invention. The catalystcompositions of Examples 1-5 comprise cerium, cobalt, and strontium inan approximate molar ratio 0160:15:25.

FIG. 1B, the upper curve of FIG. 1, shows the concentration of CO₂ inthe exhaust gas for a soot-loaded cordierite substrate that containedapproximately 30 g/L of a catalyst composition according to anembodiment of the invention. There are two peaks in CO₂ concentrationwith the sample comprising 30 g/L of catalyst at approximately 345° C.and approximately 580° C. The low temperature peak for the blank sampleoccurred at approximately 550° C. Although a high temperature CO₂ peakis not observed for the blank sample in FIG. 1, the presence of a secondhigh temperature peak is suggested by the rise in the CO₂ concentrationat the right hand side of FIG. 1. If a high temperature peak is presentin the blank sample, it may occur at a temperature of greater than 650°C.

The low temperature peak for the sample that comprised 30 g/L of thecatalyst according to an embodiment of the present invention occurred atapproximately 345° C., compared to approximately 550° C. for the blanksample that did not contain a catalyst composition according to anembodiment of the invention. Adding a catalyst composition according toan embodiment of the invention to the sample lowered the temperature ofthe low temperature CO₂ peak by about 205° C.

Further, the CO₂ concentration in the low temperature peak for thesample containing a loading of 30 g/L of a catalyst compositionaccording to an embodiment of the invention was about 220 ppm, comparedto about 50 ppm for the blank sample that did not contain a catalystcomposition according to an embodiment of the invention. The amount ofCO₂ in the exhaust gas may be a measure of the amount of particulatematter that is oxidized. High levels of CO₂ in the exhaust gas mayindicate more complete oxidation of the particulates than when lowlevels of CO₂ are present in the exhaust gas.

The increased amount of CO₂ in the exhaust gas and the lower burn offtemperature for the sample with the catalyst composition according to anembodiment of the invention are showings of the effectiveness of thecatalyst composition in increasing the rate and the effectiveness of theoxidation of the particulate matter.

Some of the CO₂ in the offgas in the low temperature peak for the blankmay be due to oxidation of the particulates by NO₂ rather than O₂. TheNO₂ in the offgas may react more readily with the particulates than doesthe O₂ in the exhaust gas. More information is needed to determine howmuch of the particulates are oxidized by the NO₂ and how much areoxidized by O₂. O₂ and NO₂ may both be oxidizing gases. It is believedthat NO may also be an oxidizing gas in the presence of the catalystaccording to embodiments of the present invention.

Example 2 Effect of Catalyst Loading on the CO₂ Concentration in theOffgas

FIG. 2 shows a series of curves for the concentration of CO₂ versustemperature for substrates with various loadings of a catalyst accordingto an embodiment of the invention. All of the loadings are on the basisof the oxides.

Curve 2A is a curve for a substrate with a catalyst loading of 5 g/L,curve 2B for a catalyst loading of 10 g/L, curve 2C for a catalystloading of 30 g/L, curve 2D for a catalyst loading of 60 g/L, curve 2Efor a catalyst loading of 90 g/L, and curve 2F is a curve for a blank, asubstrate that does not contain a catalyst.

As shown in curve 2A, the low temperature CO₂ peak for a substrate witha catalyst loading of 5 g/L occurred at about 450° C., compared to about550° C. in the blank (curve 1A). Increasing the catalyst loading to 10g/L decreased the temperature of the low temperature peak to about 425°C., as shown in curve 2B. Increasing the catalyst loading from 5 g/L to10 g/L decreased the peak temperature by about 25° C. The CO₂concentration in the low temperature CO₂ peak with the catalyst loadingof 10 g/L was 140 ppm, compared to 130 ppm for a catalyst loading of 5g/L. A catalyst loading of 10 g/L on the CDPF was more effective atcatalyzing oxidation of the particulate matter than a catalyst loadingof 5 g/L, as shown by the lower temperature of the low temperature CO₂peak and the higher CO₂ concentration in the low temperature peak withthe higher catalyst loading.

As shown in curve 2C, further increasing the catalyst loading to 30 g/Lled to a decrease in temperature of the low temperature CO₂ peak toabout 345° C., a decrease of about 60° C. from the peak temperature of405° C. for a catalyst loading of 10 g/L. Further, the CO₂ concentrationin the low temperature peak increased from about 140 ppm to about 270ppm with the higher catalyst loading of 30 g/L.

Further increasing the loading from 30 g/L to 60 g/L led to a decreasein the peak temperature of the low temperature CO₂ peak from about 345°C. to about 330° C., as shown by curve 2D, a decrease of about 15° C. inthe peak temperature with a doubling of the catalyst loading. Theconcentration of CO₂ in the offgas increased from about 270 ppm to about380 ppm when the catalyst loading was increased from 30 g/L to 60 g/L.

Further increasing the catalyst loading from 60 g/L in curve 2C to 90g/L in curve 2D did not significantly change the temperature at whichthe low temperature peak occurred. The effectiveness of the catalyst mayplateau at catalyst loadings between 60 g/L and 90 g/L, at least for thecatalyst formulations that were used in the examples. Although notwishing to be bound to a theory, it is believed that sintering of thecatalyst may take place when catalyzed diesel particulate filters withhigh catalyst loadings, for example, 90 g/L, are subjected to hightemperatures. The optimal loading of the catalyst composition on theCDPF may depend on a tradeoff between the desired reduction in ignitiontemperature and increased oxidation of SOF and SOL as the loading of thecatalyst composition is increased versus the increased cost for thehigher catalyst loading.

Beneficial effects may be seen for catalyst loadings as low asapproximately 5 g/L and up to approximately 60 g/L. Further increasingthe catalyst loading to 90 g/L may not improve the activity. A catalystloading in the range of 10-60 g/L may provide significant enhancement inoxidation of the SOF and SOL with a minimal degree of catalystsintering. The optimal catalyst loading may depend on the substrate, thecatalyst, and the operating conditions.

Example 3 Surface Areas and Pore Volumes of Aluminum Oxide WashcoatsPrepared from Aluminum Nitrate and Colloidal Alumina

FIG. 3 shows graphs of the BET surface areas in m²/g versus targetloading in g/L for aluminum oxide washcoats prepared from aluminumnitrate and colloidal alumina.

Curve 3A of FIG. 3 shows a graph of the BET surface area versus loadingfor the aluminum oxide washcoats prepared from aluminum nitrate. Curve3B of FIG. 4 shows a graph of the surface area versus loading foraluminum oxide washcoats prepared with NYACOL® AL20 colloidal alumina.

As shown in curve 3A, the BET surface area of a substrate that comprisedalumina washcoats prepared from aluminum nitrate decreased from about 8m²/g to about 3 m²/g as the target loading was increased from 0 to about40 g/L. The BET surface areas with alumina washcoats that were preparedwith colloidal alumina were higher than the BET surface areas of thecorresponding alumina washcoats that were prepared with aluminum oxideprepared from aluminum nitrate at all loadings of aluminum oxide.

In contrast, as shown in curve 3B, the BET surface area for a substrateloaded with an alumina washcoat prepared with NYACOL® AL20 colloidalalumina increased from 8 m²/g to 22 m²/g as the target loading wasincreased from 0 to 65 g/L.

FIG. 4 shows similar plots of the pore volume in cm³/g versus targetloading in g/L for washcoats comprising aluminum oxide prepared fromaluminum nitrate and from NYACOL® AL20 colloidal alumina. Curve 4A is acurve for the washcoat comprising aluminum oxide prepared from aluminumnitrate. Curve 4B is a curve for the washcoat comprising colloidalalumina. As shown in curve 4A, the pore volume of washcoats preparedfrom aluminum nitrate decreased from 0.28 cm³/g to 0.008 cm³/g as thetarget loading increased from 0 to 40 g/L.

In contrast, as shown in curve 4B, the pore volume for aluminum oxidewashcoats prepared with NYACOL® AL20 colloidal alumina increased from0.28 cm³/g to 0.58 cm³/g as the loading increased from 0 to 65 g/L. Thepore volumes with alumina washcoats that were prepared with colloidalalumina were higher than the pore volumes of the corresponding aluminawashcoats that were prepared with aluminum oxide prepared from aluminumnitrate at all loadings of aluminum oxide, as shown in FIG. 4.

The BET surface areas and pore volumes of the washcoats prepared withaluminum oxide comprising colloidal alumina were higher than the surfaceareas and pore volumes of the washcoats prepared with aluminum oxideprepared from aluminum nitrate.

Preparing washcoats from colloidal alumina rather than aluminum oxideprepared from aluminum nitrate may provide washcoats with higher surfaceareas and higher pore volumes than washcoats prepared with aluminumoxide prepared from aluminum nitrate. High surface areas and porevolumes may generally be desirable characteristics for washcoats.Washcoats prepared with colloidal alumina may therefore have advantagesover washcoats prepared with aluminum oxide prepared from aluminumnitrate.

Example 4 Hydrothermal Stability of the Catalyst Composition

FIG. 5 shows a series of curves for the CO₂ concentration in the exhaustgas versus temperature for soot-loaded substrates. Curve 5A is a curvefor a blank, a substrate with no catalyst. Curve 5B is a curve for asubstrate with a loading of 30 g/L of a catalyst composition accordingto an embodiment of the invention. Curve 5C is a curve for a substratewith a loading of 30 g/L of a catalyst composition according to anembodiment of the invention after hydrothermal aging at 850° C. for 16hours.

Hydrothermal aging involves the following procedure. The catalyst wasplaced in an oven in a 10% H₂O/air atmosphere at 850° C. for 16 hours.The catalyst was removed from the oven and was allowed to cool to roomtemperature in air.

The low temperature CO₂ peak for the blank sample occurred at about 550°C. The low temperature CO₂ peak for the substrate with the freshcatalyst composition according to an embodiment of the present inventionoccurred at about 340° C., about 210° C. lower than the peak for theblank.

The CO₂ concentration in the exhaust gas for the blank was about 0-50ppm, compared to about 220 ppm for the substrate with a loading of about30 g/L of the catalyst according to an embodiment of the invention. Highlevels of CO₂ in the exhaust gas may be an indication of more completeoxidation of the particulates on the substrate. The catalyst accordingto an embodiment of the invention was effective at catalyzing theoxidation of the particulates with the oxidizing gases, as shown by thehigher CO₂ levels in the exhaust gas with the catalyst according toembodiments of the present invention.

Curve 5C shows the curve of CO₂ concentration versus temperature for asubstrate with a loading of about 30 g/L of a catalyst compositionaccording to an embodiment of the invention after hydrothermal aging at850° C. for 16 hours. As shown in FIG. 5, the activity of thehydrothermally aged catalyst may not be significantly different from theblank.

Hydrothermal aging significantly lowered the effectiveness of the CDPFin catalyzing the oxidation of particulates.

Example 5 Hydrothermal Stability of the Catalyst Composition in thePresence of Alumina

FIG. 6 shows a series of graphs of the CO₂ concentration in ppm versustemperature for soot loaded substrates. Curves 6A, 6B, and 6C are thesame as curves 5A, 5B, and 5C and are curves for a blank substrate, asubstrate with fresh catalyst (a fresh CDPF), and a hydrothermally agedCDPF.

Curve 6D is a curve for a substrate that had been impregnated in twostages. The substrate was impregnated with AL20 (colloidal NYACOL® AL20)in a first stage and with an aqueous solution containing a catalystcomposition according to an embodiment of the invention in a secondstage.

Curve 6E is a curve for a substrate that was impregnated with AL20 andan aqueous solution of the catalyst composition according to anembodiment of the invention in two stages, as for curve 6D, afterhydrothermal aging.

Curve 6F is a curve for a substrate impregnated in a single stage with asolution containing both AL20 and a solution of the catalyst compositionaccording to an embodiment of the invention.

Curve 6G is a curve for a substrate that was impregnated in a singlestage with AL20 and a solution of a catalyst composition according to anembodiment of the invention after hydrothermal aging.

The data are summarized in Table 1 below. The last column, labeled Ratioof CO₂ After Hydrothermal Aging is the ratio of the concentration of CO₂in the low temperature peak after hydrothermal aging of the sample tothe concentration of CO₂ in the low temperature peak before aging of thesample. The last column provides a measure of how stable the CDPF istoward hydrothermal aging. A high “Ratio of CO₂ After HydrothermalAging” is a showing of a CDPF that is stable toward hydrothermal aging.

TABLE 1 Summary of Hydrothermal Aging Data, With and Without AL20 Hydro-Low Temp. CO₂ CO₂ (ppm) Ratio of CO₂ thermally Peak Temp In Low AfterCurve Sample Type Aged? (° C.) Temp. Peak Hydrothermal Aging 6A Blank No550 55 — 6B Catalyst Only No 340 230 — 6C Catalyst Only Yes 330 45 20 6DAL20 + Catalyst No 350 230 — (Two Stage Impregnation) 6E AL20 + CatalystYes 380 125 54 (Two Stage Impregnation) 6F AL20 + Catalyst No 325 270 —(Single Stage Impregnation) 6G AL20 + Catalyst Yes 330 140 52 (SingleStage Impregnation)

The temperatures of the low temperature CO₂ peak before and afterhydrothermal aging were 340° C. and 330° C. for the catalyst alone(curves 6B and 6C), 350° C. and 380° C. for the catalyst and AL20 withthe two stage impregnation, and 325° C. and 340° C. for the catalyst andAL20 with a single stage impregnation (curves 6F and 6G). Thetemperature at which the low temperature CO₂ peak occurred therefore didnot change significantly with hydrothermal aging of the CDPF.

There were large differences in the CO₂ content of the low temperaturepeak before and after hydrothermal aging, however. The CO₂ content ofthe low temperature peak for the substrate with the catalyst alone (withno aluminum oxide) was 220 ppm before hydrothermal aging and 45 ppmafter hydrothermal aging (curves 6B and 6C). The CO₂ concentration inthe low temperature peak after hydrothermal aging was only 20% of theCO₂ concentration for the substrate with the fresh catalyst. Thecatalyst suffers significant deactivation when exposed to hydrothermalaging.

The CO₂ concentrations in the low temperature peak for the substratewith the catalyst and AL20 with the two stage impregnation before andafter hydrothermal aging were 230 ppm and 125 ppm, respectively (curves6D and 6E). The hydrothermally aged sample with the two stagecatalyst/AL20 impregnation retained 54% of its fresh activity afterhydrothermal aging.

Similarly, the CO₂ concentrations in the low temperature peak for thefresh and hydrothermally aged sample with the catalyst and AL20impregnated in a single stage were 270 ppm and 140 ppm, respectively(curves 6E and 6F). The sample with the catalyst and AL20 impregnated ina single stage retained 52% of its fresh activity after hydrothermalaging, compared to 20% activity retention for the substrate with thecatalyst composition that did not comprise aluminum oxide.

The two samples that were impregnated with AL20 and a catalystcomposition according to an embodiment of the invention retained 54% and48% of the activity of the fresh sample after hydrothermal aging,compared to only 20% for the sample with the catalyst without alumina.The samples that comprised colloidal alumina were significantly morestable to hydrothermal aging than the sample with the catalystcomposition alone. The AL20 alumina in the washcoat may stabilize theCDPF toward hydrothermal aging. The improved resistance of the CDPF withthe addition of alumina is a significant improvement and an advance overconventional CDPF's.

Example 6 Typical Preparation of a Catalyzed Diesel Particulate Filter

The following example is a typical preparation for a catalyzed dieselparticulate filter according to an embodiment of the present invention.Although the substrate that was used in Example 6 was larger than thesubstrates that were used in Examples 1-5, the following preparation isotherwise a typical preparation.

A corderite DPF substrate from Coming with 200 cells per square inch wasused in the preparation. The substrate was 5.66″ in diameter and 6″long.

A slurry of 500 g of colloidal alumina (Nyacol AL20® was formed. Thealumina slurry was placed on the walls of the DPF filter using a vacuumdosing system known to those skilled in the art. After drying at roomtemperature with an air blower, the wash-coated substrate was calcinedin air at 550° C. for 4 hours. The weight of the alumina on thesubstrate after heat-treatment was 75.5 g, which corresponded to 30.2g/L of wash-coat loading.

A total of 695.2 g of Ce(NO₃)₃ solution (27.5 wt % of Ce₂O₃), 83.45 g ofCo(NO₃)₂)×6H₂O, and 101.15 g Sr(NO₃)₂ in 150 g H₂O were mixed to form ahomogenous solution having a Ce/Co/Sr molar ratio of 60/15/25. A totalof 665 of solution were impregnated into the DPF having the aluminawash-coat A total of 566 g of solution was deposited on the DPF. Afterdrying at room temperature with an air-blower, the substrate wascalcined at 550° C. for 4 hours. Weight of the cerium, cobalt andstrontium components after heat-treatment deposited on the substrate was64 g, which corresponded to a total catalyst loading of 25.6 g/L. Thecatalyst does not contain platinum group metals (PGMs).

The present invention may be embodied in other specific forms withoutdeparting from its essential characteristics. The described embodimentis to be considered in all respects only as illustrative and not asrestrictive. The scope of the present invention is, therefore, indicatedby the appended claims rather than by the foregoing description. Allchanges which come within the meaning and range of the equivalence ofthe claims are to be embraced within their scope.

1-19. (canceled)
 20. A method of removing particulates from exhaust gasfrom a diesel engine, said method comprising contacting said exhaust gaswith a catalyzed diesel particulate filter, thereby removing saidparticulates from the exhaust gas, wherein said catalyzed dieselparticulate filter comprises: a substrate; and a catalyst compositioncomprising: a) at least one first component selected from the groupconsisting of cerium and a lanthanide; and b) at least one secondcomponent selected from the group consisting of cobalt, copper,manganese and mixtures thereon, wherein said first component and saidsecond component are in an oxide form, and further wherein the catalystcomposition does not comprise metal sulfates and platinum group metals.21. The method of claim 20, wherein: a) when second component comprisescobalt, a molar ratio of the first component to the second component isin a range of 35-70:5-45; and b) when said second component comprisesmanganese, a molar ratio of the first component to the second componentis in a range of 15-60:30-70.
 22. The method of claim 20, wherein aloading of said catalyst composition on said catalyzed dieselparticulate filter is in a range of approximately 10 g/L toapproximately 60 g/L, wherein the loading is on the basis of the oxides.23. The method of claim 20, wherein said catalyzed diesel particulatefilter further comprises a washcoat.
 24. The method of claim 23, whereinsaid washcoat comprises aluminum oxide.
 25. The method of claim 24,wherein said washcoat further comprises at least one oxide selected fromthe group consisting of silica alumina, a zeolite, silica, cerium oxide,lanthanide oxide, zirconium oxide, and mixtures thereof.
 26. The methodof claim 20 further comprising removing at least a portion of saidparticulates from said catalyzed diesel particulate filter by contactingsaid catalyzed diesel particulate filter with an oxidizing gas.
 27. Themethod of claim 26, wherein said oxidizing gas is selected from thegroup consisting of O₂, NO, and NO₂.
 28. The method of claim 26, whereinsaid catalyzed diesel particulate filter is contacted with saidoxidizing gas at a temperature of approximately 100° C. to approximately800° C.
 29. The method of claim 20, further comprising contacting saidexhaust gas with a diesel oxidation catalyst, wherein contacting saidexhaust gas with said diesel oxidation catalyst is before contactingsaid exhaust gas with said catalyzed diesel particulate filter.
 30. Themethod of claim 20, wherein the catalyst composition further comprisesat least one third component comprising strontium, wherein said firstcomponent, said second component, and said third component are in anoxide form after calcination.
 31. The method of claim 30, wherein: a)when second component comprises cobalt, a molar ratio of the firstcomponent to the second component to the third component is in a rangeof 35-70:5-45: 5-35; and b) when said second component comprisesmanganese, a molar ratio of the first component to the second componentto the third component is in a range of 15-60:30-70:5-35.